Liquid bleaching composition

ABSTRACT

The present invention relates to thickened pourable aqueous bleach composition which contains abrasives, suitable for use in cleaning hard surfaces such as are found, for example, in lavatories and kitchens which are highly alkaline.

This invention relates to a pourable aqueous bleach composition whichcontains abrasives, suitable for use in cleaning hard surfaces such asare found, for example, in lavatories and kitchens.

It is particularly difficult to produce aqueous bleach stable, thickenedabrasive cleaning compositions which offer the simultaneous benefits of:good bleach stability which provides an acceptable shelf life for aproduct; acceptable viscosity characteristics; relatively low cost; andof course efficacy in removing stains and in effectively disinfectingsurfaces, especially on inclined hard surfaces such is tiled, enameledand porcelain surfaces such as are typically associated with bathroomsor kitchens. While the art provides a number of such compositionsdirected to satisfying these requirements, these compositions have notuniformly met with success. The present invention overcomes many ofthese shortcomings in the prior art.

A composition according to the invention is a stable, single phase,thickened bleach containing composition capable of adhering to verticalor inclined surfaces longer than thinner compositions. Such acomposition is effective as an agent for stain and soil removal as wellas disinfection. The high level of bleach stability and single solutionphase behavior of the composition enables the composition to have anacceptable shelf life. The compositions exhibit little or no visiblydiscernible syneresis during its normal shelf life (6-9 months) andshelf life storage conditions (20° C.). In particularly preferredembodiments the compositions exhibit little or no syneresis underaccelerated aging test conditions and at the same time exhibited goodbleach stability. Such is particularly important for use and storage ofthe product in warm climate countries (South Africa, Brazil, etc.).

The present invention provides a liquid thickened chlorine bleachcomposition comprising

-   -   an active chlorine source;    -   at least one surfactant selected from anionic surfactants, amine        oxides, and mixtures thereof;    -   at least one thickener selected from polycarboxylates,        polyacrylamides, clays, gums, cellulose derivatives, and        mixtures thereof;    -   at least one abrasive material selected from oxides, carbonates,        quartzes, siliceous chalk, diatomaceous earth, colloidal silicon        dioxide, alkali metasilicates, organic abrasive materials        selected from polyolefins, polyethylenes, polypropylenes,        polyesters, polystyrenes, acetonitrile-butadiene-styrene resins,        melamines, polycarbonates, phenolic resins, epoxies and        polyurethanes, natural materials selected from rice hulls, corn        cobs, and the like, nepheline syenite, or talc and mixtures        thereof;    -   water; and    -   optionally, one or more materials selected from perfumes and        perfume stabilizers, builders, rheology stabilizers; pH and        buffering agents, electrolytes, pigments, colorants and the        like.

Compositions according to the invention are alkaline in character,desirably having a pH of about 12 or more, exhibit very favorableviscosity characteristics, are good hard surface cleaners and featuregood bleach stability over time. The compositions may also include minoramounts, generally not more than at total of 10% wt., desirably lessthan 5% wt. of one or more optional constituents including ones whichmay improve the aesthetic appeal of the compositions, viz., perfumes andcolorants. Such optional constituents should not undesirably affect theshelf stability or rheology of the compositions.

The chlorine source can be either organic or inorganic including alkalimetal and alkaline earth metal hypohalites, hypohalite additionproducts, haloamines, haloinines, haloimides, and haloamides. These alsoproduce hypohalous bleaching species in situ. Preferred is hypochloriteand compounds producing hypochlorite in aqueous solution, althoughhypobromite is another potential halogen bleach. Those bleaching agentswhich yield a hypochlorite species in aqueous solution, include alkalimetal and alkaline earth metal hypochlorites, hypochlorites additionproducts, chloramines, chlorimines, chloramides, and chlorimides.Examples of compounds of this type include sodium, potassium, lithium,and calcium hypochlorite, monobasic calcium hypochlorite, dibasicmagnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate,potassium dichloroisocyanurate, sodium dichloroisocyanurate, sodiumdichloroisocyanurate dihydrate, trichlorocyanuric acid,1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, Chloramine T,Dichloramine T, Chloramine B and Dichloramine B.

At lower pH levels, aqueous solutions formed by dissolvinghypochlorite-yielding compounds contains active chlorine, partially inthe form of hypochlorous acid moieties and partially in the form ofhypochlorite ions. At pH levels above about 10, which is preferred forcompositions containing hypochlorite, essentially all (greater than 99%)of the active chlorine is reported to be in the form of hypochloriteion.

Most of the above-described hypochlorite-yielding bleaching agents areavailable in solid or concentrated form and are dissolved in waterduring preparation of the compositions of the instant invention. Some ofthe above materials are available as aqueous solutions.

The above-described bleaching agents are dissolved in the aqueous liquidcomponent of the present composition and are present in an active amountof from about 0.1% to 15% available chlorine.

Compositions of the present invention also include at least onesurfactant selected from anionic surfactant, amine oxides, and mixturesthereof. By way of non-limiting example useful anionic surfactantsinclude, for example, alkali metal salts, ammonium salts, amine salts,or aminoalcohol salts of one or more of the following compounds (linearand secondary): alcohol sulfates and sulfonates, alcohol phosphates andphosphonates, alkyl sulfates, alkyl ether sulfates, sulfate esters of analkylphenoxy polyoxyethylene ethanol, alkyl monoglyceride sulfates,alkyl sulfonates, olefin sulfonates, paraffin sulfonates, beta-alkoxyalkane sulfonates, alkylamidoether sulfates, alkylaryl polyethersulfates, monoglyceride sulfates, alkyl ether sulfonates, ethoxylatedalkyl sulfonates, alkylaryl sulfonates, alkyl benzene sulfonates,alkylamide sulfonates, alkyl monoglyceride sulfonates, alkylcarboxylates, alkyl sulfoacetates, alkyl ether carboxylates, alkylalkoxy carboxylates having 1 to 5 moles of ethylene oxide, alkylsulfosuccinates, alkyl ether sulfosuccinates, alkylamidesulfosuccinates, alkyl sulfosuccinamates, octoxynol or nonoxynolphosphates, alkyl phosphates, alkyl ether phosphates, taurates, N-acyltaurates, fatty taurides, fatty acid amide polyoxyethylene sulfates,isethionates, acyl isethionates, and sarcosinates, acyl sarcosinates, ormixtures thereof. Generally, the alkyl or acyl radical in these variouscompounds comprise a carbon chain containing 12 to 20 carbon atoms.

Examples of the foregoing anionic surfactants are available under thefollowing tradenames: RHODAPON, STEPANOL, HOSTAPUR, SURFINE, SANDOPAN,NEODOX, BIOSOFT, and AVANEL.

Amine oxide compounds which can be used in the present invention may bedefined as one or more of the following of the four general classes:

-   -   (1) Alkyl di (lower alkyl) amine oxides in which the alkyl group        has about 6-24, and preferably 8-18 carbon atoms, and can be        straight or branched chain, saturated or unsaturated. The lower        alkyl groups include between 1 and 7 carbon atoms, but        preferably each include 1-3 carbon atoms. Examples include octyl        dimethyl amine oxide, lauryl dimethyl amine oxide, myristyl        dimethyl amine oxide, and those in which the alkyl group is a        mixture of different amine oxides, such as dimethyl cocoamine        oxide, dimethyl (hydrogenated tallow) amine oxide, and        myristyl/palmityl dimethyl amine oxide;    -   (2) Allyl di (hydroxy lower alkyl) amine oxides in which the        alkyl group has about 6-22, and preferably 8-18 carbon atoms,        and can be straight or branched chain, saturated or unsaturated.        Examples include bis-2-hydroxyethyl) cocoamine oxide,        bis-(2-hydroxyethyl) tallowamine oxide; and bis-(2-hydroxyethyl)        stearylamine oxide;    -   (3) Alkylamidopropyl di(lower alkyl) amine oxides in which the        alkyl group has about 10-20, and preferably 12-16 carbon atoms,        and can be straight or branched chain, saturated or unsaturated.        Examples are cocoamidopropyl dimethyl amine oxide and        tallowamidopropyl dimethyl amine oxide; and    -   (4) Alkylmorpholine oxides in which the alkyl group has about        10-20, and preferably 12-16 carbon atoms, and can be straight or        branched chain, saturated or unsaturated.

While these amine oxides recited above may be used, preferred are amineoxides which may be represented by the following structuralrepresentation:

wherein

-   -   each R₁ independently is a straight chained C₁-C₄ alkyl group;        and,    -   R₂ is a straight chained C₆-C₂₂ alkyl group or an        alkylamidoalkylene having the formula    -   where R₃ is C₅-C₂₀ alkyl or        —(CH₂)_(p)—OH    -   where n is 1 to 5 and p is 1 to 6; additionally, R₂ or R₃ could        be ethoxylated (1 to 10 moles EO/mol) or propoxylated (1 to 10        moles of PO/mol).

Each of the alkyl groups may be linear or branched, but most preferablyare linear. Examples include Ammonyx® LO which is described to be as a30% wt. active solution of lauryl dimethyl amine oxide; Ammonyx® CDOSpecial, described to be a about 30% wt. active solution ofcocoamidopropylamine oxide, as well as Ammonyx® MO, described to be a30% wt. active solution of myristyldimethylamine oxide, all availablefrom Stepan Company (Northfield, Ill.) with similar materials alsoavailable from Lonza under the Barlox trademark.

Some of the aforementioned surfactants are bleach-stable but some arenot. When the composition contains a hypochlorite bleach, it ispreferable that the detergent surfactant is bleach-stable. Suchsurfactants desirably do not contain functions such as unsaturation andsome aromatic, amide, aldehydic, methyl keto or hydroxyl groups whichare susceptible to oxidation by the hypochlorite.

The surfactant component, selected from anionic surfactants, amineoxides, and mixtures thereof, is present in the compositions of thepresent invention in an amount of from about 0.1 to about 10% by weight.

At least one thickener is used in the present compositions. One exampleof thickeners contemplated herein include organic polymeric thickenersinclude polycarboxylate polymers having a molecular weight from about500,000 to about 4,000,000, preferably from about 1,000,000 to about4,000,000, with, preferably, from about 0.5% to about 4% crosslinking.Preferred polycarboxylate polymers include polyacrylate polymersincluding those sold under trade names Carbopol®, Acrysol® ICS-1 andSokalan®. The preferred polymers are polyacrylates. Other monomersbesides acrylic acid can be used to form these polymers including suchmonomers as ethylene and propylene which act as diluents, and maleicanhydride which acts as a source of additional carboxylic groups.Another example of polymeric based thickeners are those based onpolyacrylamides. One example is Solagum from Seppic.

Another class of thickeners include colloid-forming clays, for example,such as smectite and/or attapulgite types. Inorganic colloid formingclays tend to provide higher stability in the presence of chlorine anddo not thin when subjected to shear.

The clay materials can be described as expandable layered clays, i.e.,aluminosilicates and magnesium silicates. The term “expandable” as usedto describe the instant clays relates to the ability of the layered claystructure to be swollen, or expanded, on contact with water. Theexpandable clays used herein are those materials classified geologicallyas smectites (or montmorillonite) and attapulgites (or polygorskites).Smectites are three-layered clays. There are two distinct classes ofsmectite-type clays. In the first, aluminum oxide is present in thesilicate crystal lattice; in the second class of smectites, magnesiumoxide is present in the silicate crystal lattice. The general formulasof these smectites are Al₂(Si₂O₅)₂(OH)₂ and Mg₃(Si₂O₅)(OH)₂, for thealuminum and magnesium oxide type clays, respectively. It is to berecognized that the range of the water of hydration in the aboveformulas may vary with the processing to which the clay has beensubjected.

Commercially available clays include, for example, montmorillonite(bentonite), volchonskoite, nontronite, beidellite, hectorite, saponite,sauconite and vermiculite. The clays herein are available under varioustrade names such as Gelwhite H NF and Gelwhite GP from Southern ClayProducts. (both montmorillonites); Van Gel O from R. T. Vanderbilt,smectites, laponites and layered silicates from Southern Clay Products.A second type of expandable clay material useful in the instantinvention is classified geologically as attapulgite (polygorskite).Attapulgites are magnesium-rich clays having principles of superpositionof tetrahedral and octahedral unit cell elements different from thesmectites. Like the smectites, attapulgite clays are commerciallyavailable. For example, such clays are marketed under the tradenameAttagel, i.e. Attagel 40, Attagel 50 and Attagel 150 from EngelhardMinerals & Chemicals Corporation.

The thickener component may be used in amounts of about 0.1 to 10 wt -%.

Another component of the present invention is at least one abrasive.Examples of abrasive materials include oxides, carbonates, quartzes,siliceous chalk, diatomaceous earth, colloidal silicon dioxide, alkalimetasilicates, organic abrasive materials selected from polyolefins,polyethylenes, polypropylenes, polyesters, polystyrenes,acetonitrile-butadiene-styrene resins, melamines, polycarbonates,phenolic resins, epoxies and polyurethanes, natural materials selectedfrom rice hulls, corn cobs, and the like, nepheline syenite, or tale andmixtures thereof. The particle size of the abrasive agent can range fromabout 1 μm to about 1000 μm, preferably between about 10 μn to about 200μm, and more preferably between about 10 μm and about 100 μm. It ispreferred to us those abrasive agents that will not scratch glass orceramic surfaces. Such abrasive agents include calcium carbonate,siliceous chalk diatomaceous earth, colloidal silicon dioxide, sodiummetasilicate, talc, and organic abrasive materials. Calcium carbonate ispreferred. The amount of abrasive material can range from about 5 toabout 30 wt %.

As noted the compositions may also include minor amounts, generally notmore than at total of 10% wt., desirably less than 5% wt. of one or moreoptional constituents including ones which may improve the aestheticappeal of the compositions, viz., perfumes and colorants. Such optionalconstituents should not undesirably affect the shelf stability orrheology of the compositions. By way of non-limiting example suchfurther constituents include one or more coloring agents, fragrances andfragrance solubilizers, viscosity modifying agents, other surfactants,pH adjusting agents and pH buffers including organic and inorganicsalts, optical brighteners, opacifying agents, hydrotropes, antifoamingagents, enzymes, anti-spotting agents, anti-oxidants, preservatives, andanti-corrosion agents. When one or more of the optional constituents isadded, i.e., fragrance and/or coloring agents, the esthetic and consumerappeal of the product is often favorably improved. The use and selectionof these optional constituents is well known to those of ordinary skillin the art.

EXAMPLES

For purposes of illustration of the present inventive compositions,various formulations were produced and are reported below.

Into a suitably sized vessel, a measured amount of room temperaturewater (˜20° C.) was provided after which measured amounts of remainingconstituents were added. All of the remaining constituents weresimilarly supplied at room temperature; mixing of the constituents wasachieved by the use of a magnetic stirrer apparatus. Mixing, whichgenerally lasted several minutes, and maintained until the particularexemplary formulation appeared to be homogeneous.

It is to be noted that the constituents may be added in any order. Insome instances, the thickener is added first and then followed by waterto form a thickened system to which the other components are added andin other instances, a premix of water and thickener is made which isthen added to another mixture which contains the remaining components.

Exemplary inventive formulations according to the present inventionincluding certain specifically preferred embodiments are shown inTable 1. The quantities of composition components are given aspercentages by weight (wt %). Unless otherwise noted, the components inTable 1 are at 100% active. TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6Components Wt % Wt % Wt % Wt % Wt % Wt % DI Water 41.28 39.33 36.3339.28 30.00 33.00 Carbopol 676 (1.5%) 26.67 26.67 26.67 26.67 30.0030.00 Oxy-Rite 100 0.05 0.05 13.00 Gelwhite H NF (5%) 10.00 10.00 10.0010.00 10.00 Sodium Hydroxide (50%) 1.50 1.50 1.50 1.50 1.50 1.50 SodiumHypochlorite (16%) 7.00 7.00 7.00 7.00 7.00 7.00 Calcium Carbonate 10.0012.00 15.00 12.00 15.00 15.00 Ammonyx MO 1.00 1.00 1.00 1.00 1.00 1.00Genopur BK 2.50 2.50 2.50 2.50 2.50 2.50 Total 100.00 100.00 100.00100.00 100.00 100.00

TABLE 1 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Components Wt % Wt % Wt %Wt % Wt % Wt % DI Water 23.50 42.00 43.00 39.50 43.00 33.33 Gelwhite GP(5%) 10.00 5.00 5.00 3.00 5.00 15.00 Carbopol 676 (1.5%) 42.00 33.0030.00 35.00 33.00 26.67 Sodium Hydroxide (50%) 1.50 1.50 1.50 1.50 1.501.50 Sodium Hypochlorite 7.00 7.00 7.00 7.00 7.00 7.00 Calcium Carbonate12.50 9.00 10.00 10.00 7.00 12.00 Titanium Dioxide 0.50 0.50 Ammonyx MO1.00 1.00 1.00 1.00 1.00 1.00 Genopur BK 2.50 1.50 2.50 2.50 2.00 3.50Total 100.00 100.00 100.00 100.00 100.00 100.00

TABLE 1 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18 Components Wt % Wt %Wt % Wt % Wt % Wt % DI Water 36.33 38.00 41.33 28.50 33.50 27.00Carbopol 676 (1.5%) 26.67 30.00 26.67 45.00 40.00 30.00 Gelwhite H NF(5%) 15.00 10.00 10.00 16.00 Sodium Hydroxide (50%) 1.50 1.50 1.50 1.001.00 1.00 Sodium Lauryl Ether Sulfate 1.50 1.50 1.50 Sodium Carbonate0.50 Sodium Silicate 1.00 1.00 Sodium Hypochlorite (16%) 7.00 7.00 7.007.00 7.00 7.00 Calcium Carbonate 10.00 10.00 10.00 15.00 15.00 16.00Ammonyx MO 1.00 1.00 1.00 1.00 1.00 1.00 Genopur BK 2.50 2.50 2.50 Total100.00 100.00 100.00 100.00 100.00 100.00

TABLE 1 Ex. 19 Ex. 20 Ex. 21 Ex. 22 Ex. 23 Ex. 24 Components Wt % Wt %Wt % Wt % Wt % Wt % DI Water 41.33 10.00 19.00 36.00 10.00 20.03Carbopol 676 (1.5%) 26.67 30.00 54.00 35.00 10.00 26.67 Van Gel O 50.00Mineral Colloid BP 30.00 Laponite (4%) 37.50 Gelwhite H NF (5%) 10.001.00 5.00 Sodium Hydroxide (50%) 1.50 1.00 2.00 1.50 1.00 0.30 SodiumCarbonate 1.00 1.00 Sodium Hypochlorite (16%) 7.00 7.00 7.00 7.00 7.007.00 Sodium Lauryl Ether Sulfate 1.00 1.00 Calcium Carbonate 10.00 12.0015.00 12.00 20.00 15.00 Ammonyx MO 1.00 1.00 Biosoft D-40 1.50 2.00Genopur BK 2.50 2.50 Total 100.00 100.00 100.00 100.00 100.00 100.00

TABLE 1 Ex. 25 Ex. 26 Ex. 27 Ex. 28 Ex. 29 Ex. 30 Components Wt % Wt %Wt % Wt % Wt % Wt % DI Water 36.33 33.00 33.00 50.33 20.00 17.50Gelwhite GP (5%) 15.00 15.00 15.00 Solagum SF 306 1.00 Laponite (5%)28.00 30.00 Carbopol 676 (1.5%) 26.67 30.00 30.00 26.67 30.00 30.00Sodium Hydroxide (50%) 1.50 1.50 1.50 1.50 1.50 1.50 Sodium Hypochlorite(16%) 7.00 7.00 7.00 7.00 7.00 7.00 Calcium Carbonate 10.00 10.00 10.0010.00 10.00 10.00 Ammonyx MO 1.00 1.00 1.00 1.00 3.50 Genopur BK 2.500.50 Sodium Lauryl Ether Sulfate 2.50 2.50 2.50 3.50 Total 100.00 100.00100.00 100.00 100.00 100.00

TABLE 2 DI Water Deionized water Carbopol 676 (1.5%) Highly cross-linkedpolyacrylate polymer (Noveon; 100% active; added as 1.5% active solutionin water Oxy-Rite 100 Aromatic based rheological stabilizer (Noveon;100% active) Gelwhite H NF (5%) Montmorillonite (Southern Clay Products,Inc.; 100% active; added as 5% active solution in water) SodiumHydroxide (50%) Sodium hydroxide (50% active solution in water) SodiumHypochlorite (16%) Sodium hypochlorite (16% active solution in water)Calcium Carbonate Calcium carbonate Ammonyx MO Myristyldimethylamineoxide (Stepan; 30% active) Genopur BK Mixture of anionic surfactants(Clariant) Gelwhite GP (5%) Montmorillonite (Southern Clay Products,Inc.; 100% active; added as 5% active solution in water) TitaniumDioxide Titanium oxide Sodium Lauryl Ether Sulfate Sodium lauryl ethersulfate Sodium Carbonate Sodium carbonate Sodium Silicate Sodiumsilicate Van Gel O Hydrated magnesium aluminum silicate (smectite) clay(R T Vanderbilt) Mineral Colloid BP high purity montmorillonite(Southern Clay Products, Inc.; 100% active) Laponite (4%); Laponite (5%)Synthetic layered magnesium silicate (Southern Clay Products, Inc.; 100%active; added as a 4% (or 5%) active solution in water) Biosoft D-40Sodium linear alkylbenzene sulfonate (Stepan; 38% active) Solagum SF 306Polyacrylamide co-polymer (Seppic)

The compositions of the present invention are expected to have goodcleaning and/or disinfecting properties as described herein.

1. A liquid thickened chlorine bleach composition comprising: an activechlorine source; at least one surfactant selected from anionicsurfactants, amine oxides, and mixtures thereof; at least one thickenerselected from polycarboxylates, polyacrylamides, clays, gums, cellulosederivatives, and mixtures thereof; at least one abrasive materialselected from oxides, carbonates, quartzes, siliceous chalk,diatomaceous earth, colloidal silicon dioxide, alkali metasilicates,organic abrasive materials selected from polyolefins, polyethylenes,polypropylenes, polyesters, polystyrenes, acetonitrile-butadiene-styreneresins, melamines, polycarbonates, phenolic resins, epoxies andpolyurethanes, natural materials selected from rice hulls, corn cobs,and the like, nepheline syenite, or talc and mixtures thereof; water;and optionally, one or more materials selected from perfumes and perfumestabilizers, builders, rheology stabilizers; pH and buffering agents,electrolytes, pigments, colorants and the like.
 2. The compositionaccording to claim 1 wherein the surfactant is an amine oxide.
 3. Thecomposition according to claim 1 wherein the surfactant is a mixture ofanionic surfactant and amine oxide.
 4. The composition according toclaim 1 wherein the anionic surfactant is selected from alkyl sulfatesand alkyl ether sulfates.
 5. The composition according to claim 1wherein the anionic surfactant is selected from alkyl ether sulfates. 6.The composition according to claim 1 wherein the thickener is a mixtureof polycarboxylates and clays.
 7. The composition according to claim 1wherein the thickener is a mixture of polycarboxylates andpolyacrylamides.
 8. The composition according to claim 1 wherein thethickener is a polycarboxylates.
 9. The composition according to claim 1which contains a rheology modifier.
 10. The composition according toclaim 1 wherein the pH of the composition is 12 or greater.
 11. Thecomposition according to claim 1 wherein the active chlorine source is ahypochlorite bleach, and the surfactant does not comprise unsaturations.12. The composition according to claim 1 wherein the active chlorinesource is a hypochlorite bleach, and the surfactant does not comprisealdehydic, methyl keto or hydroxyl groups susceptible to oxidation bythe hypochlorite.
 13. (canceled)